JP5696390B2 - Aqueous paint composition - Google Patents

Description

  The present invention relates to an aqueous paint composition suitably used for watercolor paints, poster colors and the like.

In general, water-based paint compositions such as watercolor paints and poster colors are compositions containing water, a water-soluble resin, and a coloring material, and are applied to paper or the like when drawing a picture. Normally, watercolor paints are water as the main solvent, so when applied on the painted surface of an oily solid drawing material such as a crayon pass, the paint will repel the painted surface of the oily solid drawing material, resulting in an oily solid drawing material. Even if it is applied on the painted surface, it is possible to express that the painted surface of the underlying oil-based solid drawing material is exposed, and it is possible to overcoat the painted surface.
However, since the water-based paint contains at least a water-soluble resin and water, it has the disadvantage that molds are generated over time and spoilage bacteria are propagated. Therefore, the use of a preservative and a fungicide is indispensable.

  Patent Document 1 describes an aqueous pigment composition containing at least a pigment, a resin, a wetting agent, water, and phenoxyethanol and sodium fluoride as preservatives, as an antiseptic or fungicide added to an aqueous paint composition. Has been. Patent Document 2 describes an aqueous pigment composition containing at least a pigment, a resin, a wetting agent, orthophenylphenol or a salt thereof as a preservative, trichlorohydroxydiphenyl ether, and phenoxyethanol.

JP 2006-036966 A JP 2002-322406 A

Preservatives and fungicides are highly reactive, especially hydrophilic preservatives, because they have the effect of inhibiting the growth of fungi and fungi by destroying bacterial and fungal cell membranes and causing cellular respiratory disorders. Often reacts with water-soluble polymers and causes problems such as discoloration.
On the other hand, lipophilic antiseptics and fungicides such as those described above have little reactivity with water-soluble polymers, but because of the inclusion of lipophilic components in the paint, they are easy to adjust to oil and repel water. So, when painted on the painted surface of oily solid drawing materials such as crayons and passes, the painted surface of oily solid drawing materials is hidden without being repelled, even though it is a water-based paint. When it is overcoated on its own coating film, it is repelled and cannot be applied cleanly.

The present invention contains at least a glycol solvent selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol , 3-iodo-2-propynyl butyl carbamate, a pigment, a water-soluble resin, and water. A water-based paint composition is used as a gist.

  3-Iodo-2-propynylbutyl carbamate does not dissolve in water and has lipophilic properties, but when used in combination with a glycol solvent, the vicinity of the ketone group at the center of 3-iodo-2-propynylbutyl carbamate and a glycol solvent Since one of the hydroxyl groups of the 3-amino-2-propynyl butyl carbamate is covered with the ketone group as the center, the lipophilic nature of 3-iodo-2-propynyl butyl carbamate is due to the hydrophilicity of the glycol solvent. When it is applied on the painted surface of oily solid drawing material such as crayons and passes, it repels the painted surface of oily solid drawing material and repels it when it is overcoated on its own coating film. In addition, when it comes into contact with mold or fungus, the iodine group is at the end of 3-iodo-2-propynyl butyl carbamate, so that glycol solvent is not contained. It passes to be considered and it is possible to demonstrate the efficacy of antiseptic and antifungal.

  Water is used as the main solvent in the aqueous paint composition.

  The pigment is used as a colorant, and conventionally known titanium dioxide, titanium black, zinc oxide, carbon black, iron black, aniline black, Hansa Yellow-10G, 5G, 3G, R, G, Benzidine Yellow G, Benzidine Yellow 5G, Benzidine Yellow 8G, Permanent Yellow NCG, Quinoline Yellow, Permanent Orange 2G, Indanthrene Brilliant Orange GK, Vulcan Orange, Pyrazoline Orange TMP, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red , Brilliant carmine BS, pyrazolone red, Bordeaux 5B, thioindigo red, naphthol carmine HR, naphthol red F5RK, naphthol red F3RK-70, permanent trem FGR, Permanent Carmine FB, Permanent Red 2B, Brilliant Carmine 6B, Watching Red, Permanent Red FRLL, Carmine Lake, Carmine FBB, Fast Violet B, Methyl Violet Lake, Induslen Violet, Induslen Blue, Acid Green Lake, Dichloro Quinacridone red, quinacridone magenta, dichloroquinacridone magenta, quinacridone violet, quinacridone scarlet, quinacridone orange, quinacridone maroon, indigo, dioxazine violet, perylene red, perylene vermilion, perylene maroon, perylene scarlet, perylene brown, perylene violet, perylene black, Perinone orange, Perinon le , Isoindolinone yellow G, isoindolinone yellow R, isoindolinone yellow 6G, isoindolinone orange, isoindoline yellow R, isoindoline yellow G, isoindoline orange, isoindoline red, DPP red, DPP orange, DPP Scarlet, DPP rubin, alkali blue, copper phthalocyanine blue, copper phthalocyanine green, first sky blue, dial, bitumen, ultramarine, Victoria blue lake, marker light green lake, pigment green B, viridian, iron oxide, iron hydroxide, Schenner , Amber, aluminum powder, bronze powder, organic pigments, inorganic pigments and metal powder pigments, colored processed powders and fluorescent pigments combining dyes and pigments with resin powders, and natural mica surfaces Can be selected and used from among those coated with a metal oxide and pearl pigments whose surface of synthetic mica is coated with a metal oxide. At this time, these pigments may be washed with water and then dried, or may be adjusted with a pH adjusting agent such as an alkaline agent, or may be used alone or in admixture of two or more. The amount used is preferably 0.1% by weight to 40% by weight with respect to the total amount of the aqueous paint composition.

  The water-soluble resin is used as a fixing agent and a color developing agent. Gives film formation ability to the handwriting or application mark by the aqueous pigment composition of the present invention, imparts adhesion performance to the writing surface and the coated surface, imparts viscosity to the aqueous pigment composition, and stabilizes dispersion of the pigment Used for the purpose of imparting sex. Any material that is soluble in water can be used. Specific examples include natural water-soluble polymers such as glue, gum arabic (Acacia Senegal, Acacia Sejar), yellow dextrin, white dextrin, and British gum, and semi-synthetic water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. Synthetic water-soluble polymers such as molecules, polyvinyl alcohol, and water-soluble acrylic resins can be used, and these may be used alone or in admixture of two or more. If the amount used is small, sufficient fixability can be imparted, and if the amount used is too large, the viscosity of the aqueous paint composition increases, so that it becomes difficult to paint, so the total amount of the aqueous paint composition is reduced. The content is preferably 1% by weight to 30% by weight.

  Examples of the glycol solvent used in the present invention include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and diethylene glycol dimethyl ether, which are liquid at 20 ° C. desirable. If the amount used is small, hydrophilicity can be sufficiently imparted to 3-iodo-2-propynylbutyl carbamate, and if the amount used is too large, the aqueous paint composition is difficult to dry. The content is preferably 0.01% by weight to 20% by weight based on the total amount of the product.

  3-iodo-2-propynylbutyl carbamate is used as an antiseptic / antifungal agent, and examples thereof include SK-IPBC (manufactured by Sanai Oil Co., Ltd.). If the amount used is small, the antiseptic and antifungal properties can be sufficiently exerted, and if the amount used is too large, the toxicity to the human body becomes strong, so the amount used is based on the total amount of the aqueous paint composition. 0.01 wt% to 2 wt% is preferable, and 0.5 wt% to 1 wt% is more preferable.

In addition to the above components, various components can be blended as necessary.
In order to adjust the drying speed of the aqueous paint composition and improve the solubility in water, a water-soluble high-boiling solvent such as glycerin can also be used. The amount used is preferably 1% by weight to 20% by weight with respect to the total amount of the aqueous paint composition. Also, water-soluble such as chloroacetamide, 2-pyridinethiol-1-oxide / sodium salt, sodium dehydroacetate, sodium benzoate, sodium sorbate, potassium sorbate, 2-bromo-2-nitropropane-1,3-diol White inorganic powders such as calcium carbonate, talc, mica, silica, kaolin clay, alumina silica, and precipitated barium sulfate can be used in combination as an antiseptic / antifungal agent and extender. Regardless of the particle diameter, shape, and pH of these white inorganic powders, they may be used alone or in combination of two or more. Of course, it can be used in combination with a rust inhibitor, a defoaming agent, an antifoaming agent, a surfactant, and the like.

The aqueous paint composition of the present invention can be easily obtained by mixing and dispersing the above components with a conventionally known stirring and dispersing machine such as a turbo mixer, a Henschel mixer, a three-roll mill, a horizontal ball mill, or a horizontal bead mill. .
In addition, a water-soluble resin solution prepared by stirring water and preservatives with a stirrer such as a turbo mixer is used, and then other components are added and mixed and dispersed. 3-Iodo-2-propynyl butyl carbamate glycol solvent dispersion prepared by mixing and dispersing propylene glycol and other glycol solvents in propynyl butyl carbamate is added to the mixture of other components and mixed and dispersed later. May be.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example.

Example 1 Watercolor Paint Titanium Dioxide 2 parts by weight C.I. I. Pigment Blue 15: 3 0.5 parts by weight C.I. I. Pigment Blue 15: 1 0.5 part by weight C.I. I. Pigment Blue 29 9 parts by weight Heavy calcium carbonate 34 parts by weight Alumina silica 5 parts by weight Arabic gum 10.5 parts by weight Yellow dextrin 6.5 parts by weight Water 24.8 parts by weight 3-Iodo-2-propynylbutyl carbamate 0.2 parts by weight Part propylene glycol 7 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a blue watercolor paint.

Example 2 Watercolor Paint Titanium Dioxide 2 parts by weight C.I. I. Pigment Yellow 55 1 part by weight C.I. I. Pigment Yellow 98 1.5 parts by weight C.I. I. Pigment Yellow 1 0.5 part by weight C.I. I. Pigment Yellow 74 2 parts by weight C.I. I. Pigment Yellow 152 0.1 parts by weight light calcium carbonate 30 parts by weight silica 2.5 parts by weight gum arabic 16.2 parts by weight yellow dextrin 3 parts by weight water 32.6 parts by weight 3-iodo-2-propynyl butyl carbamate 0.3 parts by weight Part ethylene glycol 8 parts by weight demole N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a yellow watercolor paint.

Example 3 Watercolor Paint Titanium Dioxide 2 parts by weight C.I. I. Pigment Yellow 3 10 parts by weight C.I. I. Pigment Blue 15: 3 0.1 parts by weight C.I. I. Pigment Green 7 0.1 parts by weight heavy calcium carbonate 15 parts by weight light calcium carbonate 14 parts by weight alumina silica 5 parts by weight gum arabic 11.4 parts by weight yellow dextrin 5.5 parts by weight water 25 parts by weight 3-iodo-2-propynyl Butyl carbamate 0.1 parts by weight Diethylene glycol 11.8 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a yellow-green watercolor paint.

Example 4 Watercolor Paint C.I. I. Pigment Yellow 14 2 parts by weight C.I. I. Pigment Green 7 2 parts by weight Heavy calcium carbonate 27 parts by weight Light calcium carbonate 14 parts by weight Alumina silica 2 parts by weight Yellow dextrin 19 parts by weight Sodium salt of carboxymethyl cellulose 1 part by weight Water 25.2 parts by weight 3-iodo-2-propynylbutyl Carbamate 0.5 parts by weight diethylene glycol 7 parts by weight Demol N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
(Product made) 0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a green watercolor paint.

(Example 5) Watercolor paint C.I. I. Pigment Blue 15: 1 7 parts by weight C.I. I. Pigment Red 150 0.1 parts by weight C.I. I. Pigment Violet 23 0.1 parts by weight heavy calcium carbonate 28 parts by weight silica 1.7 parts by weight gum arabic 13.2 parts by weight yellow dextrin 8 parts by weight water 32.3 parts by weight 3-iodo-2-propynyl butyl carbamate 0.2 Parts by weight ethylene glycol 8.8 parts by weight demole N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
0.6 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a blue watercolor paint.

(Example 6) Watercolor paint C.I. I. Pigment Red 48:32 2 parts by weight C.I. I. Pigment Red57 1 part by weight C.I. I. Pigment Red 170 1 part by weight light calcium carbonate 29 parts by weight silica 3.5 parts by weight gum arabic 18.2 parts by weight water 35.9 parts by weight 3-iodo-2-propynylbutyl carbamate 0.1 parts by weight propylene glycol 9 parts by weight demole N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
(Product made) 0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a red watercolor paint.

Example 7 Watercolor Paint C.I. I. Pigment Red 112 1 part by weight Existing chemical substance number 4-1055 (red pigment) 1 part by weight C.I. I. Pigment ORANGE16 2 parts by weight heavy calcium carbonate 36.5 parts by weight silica 3.5 parts by weight gum arabic 7.8 parts by weight yellow dextrin 13 parts by weight glycerin 4.5 important parts water 26.9 parts by weight 3-iodo-2- Propinylbutyl carbamate 0.5 parts by weight Ethylene glycol 3 parts by weight Demol N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a vermilion watercolor paint.

(Example 8) Watercolor paint C.I. I. Pigment Red101 8 parts by weight C.I. I. Pigment Yellow 42 1 part by weight light calcium carbonate 8.5 parts by weight heavy calcium carbonate 30 parts by weight silica 3.5 parts by weight gum arabic 14.5 parts by weight glycerin 5.3 important parts water 26.8 parts by weight 3-iodo-2 -Propinyl butyl carbamate 0.4 weight part diethylene glycol 2 weight part The said component was stirred with the turbo mixer for 15 minutes, Then, it passed twice with the 3 roll mill, and the brown watercolor paint was obtained.

Example 9 Watercolor Paint C.I. I. Pigment Black 7 3 parts by weight C.I. I. Pigment Black 9 2 parts by weight C.I. I. Pigment Black 1 1 part by weight light calcium carbonate 22 parts by weight silica 6.5 parts by weight gum arabic 13.5 parts by weight yellow dextrin 7.5 parts by weight glycerin 8.8 important parts water 26.3 parts by weight 3-iodo-2-propynyl Butyl carbamate 0.5 parts by weight Diethylene glycol 8.9 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a black watercolor paint.

(Example 10) Watercolor paint NIPPON KOKEN INDUSTRIAL CO., LTD. PEARGLIZE MRY-100 10 parts by weight NIPPON KOKEN INDUSTRIAL CO., LTD. PEARGLASE ME-100 4 parts by weight BASF MEARIN Brilliant Gold 10 parts by weight Sericite 3 parts by weight Montmorillonite 2 parts by weight Gum arabic 4.2 parts by weight Sodium salt of carboxymethyl cellulose 2.4 parts by weight Glycerin 11.9 Important parts Water 47 parts by weight 3-Iodo-2-propynylbutyl carbamate 0.4 parts by weight Propylene glycol 5 parts by weight 0.1 parts by weight of oleic acid ester of polyoxyethylene bisglycerborate The above ingredients were stirred with a turbo mixer for 30 minutes to obtain a golden watercolor paint.

(Example 11) Watercolor paint Titanium dioxide 36 parts by weight Light calcium carbonate 16 parts by weight Alumina silica 3 parts by weight Arabic gum 8.7 parts by weight White dextrin 3.7 parts by weight Glycerin 7.9 parts by weight Water 24.1 parts by weight 3 -Iodo-2-propynylbutyl carbamate 0.2 parts by weight Ethylene glycol 0.4 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a white watercolor paint.

Example 12 Watercolor Paint C.I. I. Pigment Yellow 42 20 parts by weight heavy calcium carbonate 25 parts by weight silica 3 parts by weight gum arabic 9 parts by weight yellow dextrin 10 parts by weight glycerin 3.3 important parts water 26.2 parts by weight 3-iodo-2-propynyl butyl carbamate 1 part by weight Propylene glycol 2 parts by weight Polyoxyethylene bisglycerborate oleate 0.5 parts by weight The above ingredients were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain an ocher watercolor paint It was.

Example 13 Watercolor Paint C.I. I. Pigment Blue 15: 3 1 part by weight C.I. I. Pigment Red122 2 parts by weight NKP-8377 (purple fluorescent pigment) manufactured by Nippon Fluorochemicals Co., Ltd. 8 parts by weight heavy calcium carbonate 35 parts by weight silica 2 parts by weight gum arabic 10.8 parts by weight yellow dextrin 7 parts by weight water 24.5 Part by weight 3-iodo-2-propynylbutyl carbamate 2 parts by weight Ethylene glycol 7.4 parts by weight Demol N (sodium salt of β-naphthalenesulfonic acid formalin condensate, Kao Corporation
0.3 parts by weight The above components were stirred for 15 minutes with a turbo mixer and then passed twice with a three-roll mill to obtain a purple watercolor paint.

(Comparative Example 1)
In Example 5, except that 0.2 parts by weight of 3-iodo-2-propynylbutyl carbamate and 8.8 parts by weight of ethylene glycol were added, 1 part by weight of phenoxyethanol and 0.005 parts by weight of sodium fluoride were added. In the same manner as in Example 5, a watercolor paint was obtained.

(Comparative Example 2)
In Example 2, except for 0.3 parts by weight of 3-iodo-2-propynylbutyl carbamate, 0.6 parts by weight of phenoxyethanol, 0.05 parts by weight of orthophenylphenol and 0.1 parts by weight of trichlorohydroxydiphenyl ether were added. In the same manner as in Example 2, a watercolor paint was obtained.

(Comparative Example 3)
In Example 9, except 0.5 part by weight of 3-iodo-2-propynylbutyl carbamate and 8.9 parts by weight of diethylene glycol, 0.1 part by weight of phenoxyethanol, 0.1 part by weight of orthophenylphenol and 0. 3 parts of trichlorohydroxydiphenyl ether. A watercolor paint was obtained in the same manner as in Example 9 except that 1 part by weight was added.

(Comparative Example 4)
A watercolor paint was obtained in the same manner as in Example 7 except that 3 parts by weight of ethylene glycol was removed.

  Table 1 shows the results of confirming the mold resistance test obtained in Examples 1 to 13 and Comparative Examples 1 to 3, the coatability on the oily solid drawing material coating surface, and the overcoatability.

Mold resistance test After the preparation, each water-based pigment composition within 48 hours was subjected to a wrinkle resistance test according to the method of “6. Test of paint” described in Japanese Industrial Standards (JIS Z 2911). At this time, instead of the test piece, an aqueous pigment composition was used as a sample, and the center of the medium was hollowed into a diameter of 30 mm for testing. A sample in which mycelium growth was not observed was indicated as “◯”, and a sample in which mycelium growth was observed was denoted as “x”.

Coating properties of oil-based solid drawing material on the painting surface Pentel Kureyon "Aka" (PTC-T11R), an oil-based solid drawing material, with drawing paper (basis weight 73.3 to 210 g / cubic meter, whiteness 75% or more) ). About 2 g of the aqueous pigment composition is put on a glass plate on the painted surface, and about 30% of water is added and mixed so that it is well mixed with a paint brush. After 1 minute, it was visually evaluated whether or not the paint on which the painted surface of Kureyon was repelled was repelled, and “○” was given to those that were repelled, and “X” was given to those that were not repelled.

Overcoatability About 2 g of aqueous pigment composition is put on a glass plate, and about 30% of water is added and mixed well with a paintbrush. Drawing paper (basis weight 73.3 to 210 g / cubic meter, whiteness 75% or more) ), And the coated material was dried at 37 ° C. ± 5 ° C. for 1 hour, and then about 2 g of the aqueous pigment composition was again put on the glass plate as a trace of the aqueous pigment composition. Add the amount of water and mix well with a paintbrush. Evaluate whether the paint on the bottom can be recognizable visually or not by recoating the paint on the top. The thing which has been set as "x".

As explained in Examples 1 to 13, an aqueous paint composition comprising at least a pigment, a water-soluble resin and water, and 3-iodo-2-propynylbutyl carbamate and a glycol-based solvent such as propylene glycol or ethylene glycol. By combining, it is possible to express the underlying oily solid drawing material exposed even if it is applied on the oily solid drawing material painting surface while exhibiting sufficient antifungal effect, Overpainting can be applied to the painted surface.
As in Comparative Example 1, when phenoxyethanol, which is an oily antiseptic and antifungal agent, is used, the antifungal effect is sufficient, but even if it is applied on the coating surface of the oily solid drawing material, the underlying oily solid drawing material The painted surface cannot be exposed and cannot be overpainted on its own painted surface.
In Comparative Example 2, ethylene glycol, a glycol solvent, is used in combination with orthophenylphenol, trichlorohydroxydiphenyl ether, and phenoxyethanol. Even in this case, the antifungal effect is sufficient, but on the painted surface of the oil-based solid drawing material. Even if it is applied to the surface, it cannot be expressed that the painted surface of the underlying oil-based solid drawing material is exposed, and it cannot be overcoated on its own painted surface.
In Comparative Example 3, the amount used is reduced by a combination of orthophenylphenol, trichlorohydroxydiphenyl ether and phenoxyethanol. However, even when applied on the coating surface of the oily solid drawing material, the coating of the underlying oily solid drawing material is applied. The surface cannot be exposed, and it cannot be overcoated on its own painted surface.
In Comparative Example 4, when a combination of 3-iodo-2-propynylbutyl carbamate and glycerin was used without using a glycol solvent, the oil-based solid drawing material was applied while exhibiting a sufficient antifungal effect. Even if it is applied on the drawing surface, it cannot be expressed that the painting surface of the underlying oil-based solid drawing material is exposed, and it is not possible to overcoat the own drawing surface.

Claims (1)

An aqueous paint composition containing at least a glycol solvent selected from ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol , 3-iodo-2-propynylbutyl carbamate, a pigment, a water-soluble resin, and water. object.